JPS613A - Plant blight controlling agent - Google Patents

Abstract

PURPOSE:To provide a plant blight controlling agent containing specific two kinds of compounds, exhibiting high controlling effect by the synergistic effect, having excellent residual activity and extended application period, resistant to rain, and exhibiting remarkable effect to the late blight and downy mildew spreading frequently in rainly season. CONSTITUTION:The objective agent contains (A) the compound of formula I (R is H, alkyl, halogenoalkyl, or alkenyl; X1-X3 are H, alkyl, alkoxy, halogenoalkoxy, or halogen), such as N-ethyl-N-(4-methoxyphenyl)-dichloromaleic acid diamide and (B) the compound of formula II [Ar is phenyl substituted with halogen or alkyl; R1 is alkoxyalkyl, 5- or 6-membered heterocyclic group, halogenoalkyl, etc.; R2 and R3 are alkyl or together form (CH2)n (n is 2 or 3)], such as N-(2,6-dimethylphenyl)-N-methoxyacetyl)alanine. The amount of the compound of formula II is preferably 0.3-1pt. per 1pt. of the compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to the general formula [wherein R is a hydrogen atom, a lower alkyl group, a lower halogenoak group, or a lower alkenyl group, Xl, X2. X
3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower halogenoalkoxy group, or a halogen atom, respectively] and a compound represented by the general formula [wherein Ar is a phenyl group substituted with a halogen atom or a lower alkyl group] , R1 is a lower alkoxy lower alkyl group, a 5- to 6-membered heterocyclic group containing a sulfur atom, a nitrogen atom or an oxygen atom, a lower halogenoalkyl group or a lower cycloalkyl group, and R2 and 13Fi are each a lower alkyl group. Or, R2 and R3 are combined to form the formula -(
cu2)n- (in the formula, n represents 2 or 3).

The plant disease control agent of the present invention can cause various diseases (e.g. Phytophthora secondary blight, downy mildew, It is useful as a prophylactic and therapeutic agent for diseases such as sclerotid blight, etc.) and rice blast disease.

Problems to be Solved by the Prior Art and the Invention In recent years, environmental pollution caused by pesticides such as residue in crops has become a problem, and there is a strong need for highly safe pesticides that are low in toxicity and do not accumulate in animals, plants, or soil. There is. To this end, it is desirable to reduce the amount of active ingredients in the pesticides that are applied so that they can be highly effective in controlling as many diseases as possible. Especially for various plant diseases such as late blight, downy mildew, and scab, there are almost no fungicides that have both preventive and therapeutic effects, and they are difficult to find in terms of durability and toxicity. It cannot be said to be sufficient. Compound CI) is a new compound, but compound (If) is known as shown in the following literature.

Means for Solving the Problems The present inventors have been conducting intensive research into drugs that can cause high plant disease damage with relatively small doses, and found that when compound (1) and compound (II) are used in combination, unexpected results can be found. The present inventors have discovered that they exhibit excellent preventive and therapeutic effects against various plant diseases at concentrations lower than those used as single agents.Based on these findings, and as a result of various studies, they have completed the present invention. Ta.

Compound (If) has no preventive effect against various plant diseases, and although it has a therapeutic effect on tomato late blight and cucribe, it lacks long-lasting effects, and it also has a therapeutic effect on tomato blight and cucribe.
It is completely ineffective against summer wasting disease, and in some cases does not exhibit satisfactory effects against various plant diseases, such as promoting the onset of cucumber powdery mildew.

However, when the above-mentioned compound (II) is used in combination with a compound [-I] that shows preventive effects against various plant diseases, the effect of preventing and preventing various plant diseases can be obtained at a much lower concentration than the usual concentration of each single agent. In addition to exhibiting a therapeutic effect (synergistic effect), it remains stable for a long period of time and maintains its bactericidal effect (residual effect).

Furthermore, the number of types of plant diseases that can be controlled has increased, the suitable period for use has been expanded, and there are fewer outlets for chemicals due to rain (W! #
It is highly effective in preventing and treating plant diseases such as late blight and downy mildew, which occur frequently during the rainy season.

In the above general formulas CI) and CII), R, R8゜R3
,Xl, ! 2 Also, as a lower alkyl group represented by tlx3, a lower alkyl group as a substituent in a phenyl group substituted with a lower alkyl group represented by Ar, a lower alkyl group in a lower alkoxy lower alkyl group represented by R11, for example, meth , ethμ, n-propyμ, isopropy, &, fi-butyl.

Isocrop μ, P4ee-buti μ, tert-buti ρ
A linear or branched lower chain NUN with 1 to 4 carbon atoms such as
group is used.

The lower halogenoalkyl group represented by R1R□ is
1 to 3 halogen atoms (eg, fluorine) at any position of the above-mentioned lower alkyl group.

Substituted compounds (chlorine, bromine, hydrogen) are used, and specific examples thereof include chloromethyl.

Bromomethyp, dichlorop-methyl,) lifluoromethyp,
1-chloroethylW, 2-chloroethyl μ, 2-bromoethyl, 1.2-/chloroethyl, 1-chloropropy~,
2-Chrylopropyμ, 3-bromopropyμ, 3-iodopropyμ, 1.1-dichloropropyA/, 3.3.3-
) Rikupropripi, 3,3.3-trypmopropiA
/, 1-methyl-2,2,2-tribromoethyl, 1-
Chlorobuty〃, 2-chlorobuty μ, 3-bromobuty A/
, 4-chlorobuty/1', 4,4-dichlorobutyl, 4゜4-dibromobuty/', 4.4.4-) dichlorobutyl, 4.4.4-) dibromobuty μ, 1.1-R Examples of lower alkenyl groups include vinyl, 1
Lower alkenyl groups having 2 to 4 carbon atoms such as -propenyl, 2-probenyl, 1-butenyl, 2-putenyl, 3-putenyl, 2-methy/L/-1-propenyl are used.

Lower alkoxy group represented by xl, x2 or x3, R
Examples of the lower alkoxy group as a substituent in the lower alkyl group represented by 1 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and imbutoxy.

A linear or branched lower 1-koxy group having 1 to 4 carbon atoms such as tert-butoxy is used. Specific examples of the lower 1μ koxy lower oxy group represented by R1 include methoxymethyl, ethoxymethy, n-propoxymethy, and isobutoxymethyl.

Methoxyethyl, ethoxyethyl, isopropoxyethyl, n-butoxymethy/L', 3-methoxypropy~,
Examples thereof include 3-ethoxypropyl, 2-methoxy-1-methylethyp, and 4-methoxybutyp.

A lower halogenoalkoxy group represented by Examples include alkoxy groups such as chloromethoxy,
Bromoethoxy, dichloromethoxy, diglomomethoxy, difluoromethoxy, trifluoromethoxy, 1-chloroethoxy, 2-chloroethoxy, 2-bromoethoxy, 1,2-dichloroethoxy, 1-chloropropoxy, 2-chloropropoxy, 3 -bromopropoxy, 3-
Mead probogysi, 1,1-dichloropropoquine, 3,
3.3-)lichloropropoxy, 3.3.3-tribromopropoxy, 1-chlorobutoxy, 2-chlorobutoxy, 3-glomobutoxy, 4-chlorobutoxy, 4.4
-dichlorobutoxy, 4,4-dibromobutoxy, 4.
4.4-)lichloroptoxy, 4,4.4-t')fuc
1 moft? rV, 1-jflV-2, 212-tribromoethoxy, 1,1-dimethy/L/-2,2°2-trichloroethoxy, etc. are used.

Xl, halogen atom represented by X2t or x3, Ar
Examples of the halogen atom in the phenyl group substituted with a halogen atom include fluorine, chlorine, bromine,
Iodine etc. are used.

Specific examples of the phenyl μ group substituted with halogen or lower alkyl group represented by Ar include Example LG-12-9.
0CI PhenyA', 3-chlorophenyl.

4-chlorophenyl, 2-promophenyl μ, 3-promophenyl, 4-iodophenyl A/, 2,4-dichloropheniμ, 2-methylphenyl, 4-methyμ phenyl #, 2,6-dimethy~pheniμ, 2゜5-dimechi! Fueniμ, 2.4.6-DrimethiμFueni/l', 2,
6-diethylphenyl + 4-n-propyμpheni” + 4n-butyμphenyρ, etc. 1 total.

As the lower cyclobutyl group represented by R, for example, a lower cycloalkyl group having 3 to 7 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexy, cycloheathyl and the like is used.

The heterocyclic group containing a 5- or 6-membered sulfur atom, nitrogen atom or oxygen atom represented by R1 is, for example, 2- or 3-fury, bifniμ, 2- or #i3-pyrrolyl, viridiμ, 2- or an unsaturated 5- to 6-membered heterocyclic group such as 3-chenyl: for example, 2- or 3-tetrahydrofura w=μ, 2-, 3- or 4-tetrahydrofuryl/
L', 2- or 3-pyrrolidinyl, 2-. 3- or 4- hand in hand? Saturated 5- or 6-membered heterocyclic groups such as piperidi~, 2-7F'', or 3-tetofuhio7-dorop7t/I/ are used.

Preferred compounds among compounds CI) are those in which R is a lower alkyl group, Xl, X2. Each of X3 is a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. More preferably, R is a lower alkyl group, Xl is a hydrogen atom, and X2. A combination in which X3 is a lower alkyl group or a halogen atom, respectively, or a combination in which Xl and x2 are a hydrogen atom and x3 is a lower alkoxy group.

Specifically, preferred compounds (II) include:
N-(2,6-dimethyivy=yv) -y-(methoxyacetyl A/)afnin methyl ester; N~(
2,6-dimethylphenylene/l/)-N-(2-furoyl)abunine methyl ester; 2-chloro-N~(2,
6-dimethylphene A/) -M -(tetrahydro-
2-oxo-3-furani/I/) a7doamide; and 3
-CloA/-N-(tetrahydro-2-oxo-3-furoni/L')cyclopropanecarboxyanilide.

The plant disease control agent of the present invention can be used to control various pathogenic bacteria that cause plant diseases, such as algae (Dhycomycetes).
ycetes )), Ascomycetes (Ascomycetes), Basidiomycetes (Basidiomycetes)
) and Deuteromycosis (Fun)
It has a strong control effect (preventive and therapeutic effect) against filamentous fungi such as 211mperfecti) and actinomycetes. In particular, filamentous fungi exhibit excellent control effects against filamentous fungi, such as filamentous fungi that parasitize plants and attack the aerial parts of plants.

It shows outstanding control (preventive and therapeutic) effects on filamentous fungi that are contagious from one seed and invade plants through the soil.

The plant disease control agent of the present invention is effective against various plant diseases caused by pathogenic bacteria such as filamentous fungi and actinobacteria, particularly on soybeans such as cucumbers, tomatoes, and potatoes.

It is effective in controlling various diseases of fruit trees such as peaches, grapes, and apples, as well as rice blast. Among them, downy mildew of cucumber, anthracnose, scab, and late blight of tomato.

Mildew, late blight of potatoes, black spot of pears, grapes, apples, etc., gray mold, downy mildew, seedling damping-off, clubroot, rice yellowing dwarf has a remarkable pesticidal effect.

Further, the plant disease control agent of the present invention stably exists for a considerable period of time after being treated on plants and maintains its bactericidal effect (residual effect), so that it is possible to control plant diseases over a long period of time.

The plant disease control agent of the present invention has low sensitivity to warm-blooded animals, has little impact on fish and the environment, and has extremely excellent qualities as a disinfectant composition for agricultural use.

When using the plant disease control agent of the present invention, the compound CI
) may be used in combination with two or more compounds, and one or more compounds [■] may be used in combination.

The plant disease control agent of the present invention comprises compound CI) and compound (I).
I) in a suitable liquid carrier (e.g. a solvent), or
Alternatively, it may be dispersed and mixed with or adsorbed onto a suitable solid carrier (e.g. diluent, bulking agent), and if necessary, further added with emulsifiers, suspending agents, spreading agents, penetrants, wetting agents, etc. It is used in dosage forms such as emulsions, wettable powders, and single powder tablets by adding viscous agents and stabilizers. These formulations can be prepared by known methods.

The compound [technique] in the plant disease control agent of the present invention is preferred. In addition, the weight ratio of the sum of compound CI) and compound CI[) to the entire plant disease control agent is approximately 5 to 50% by weight, but the proportion may be adjusted depending on the conditions at the time of use and the disease occurrence situation. It is also possible to change the ratio as appropriate.

When using, dilute and increase the amount with emulsion, irrigation agent, etc. (
For example, 500 to 5000 times) is recommended.

Examples of liquid carriers (solvents) used in the plant disease control agent of the present invention include water, alcohols (such as methyl alcohol, ethyl alcohol, ethylene glycol, etc.).
), ketones (e.g. acetone, methyl alcohol, etc.), Koichite/'JO (& e.g. dioxane,
aliphatic hydrocarbons (e.g. gasoline, kerosene, kerosene, fuel oil, machine oil, etc.), aromatic hydrocarbons (e.g. benzene).

toluene, xylene, solvent naphtha, methylnaphthalene, etc.), other halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, etc.), acid amides (e.g. dimethylformamide, etc.), esters (e.g. ethyl acetate, acetic acid) Solvents such as butyl esters, heptazo-, di- or triglycerin esters of fatty acids (3 to 20 carbon atoms), 2) Use one type or a mixture of two or more types.

As a solid carrier (diluent, bulking agent), physical powder (to 41) is used.
(for example, soybean powder, tobacco powder, wheat flour, wood flour, etc.), mineral powders (for example, clays such as kaolin, bentonite, and acid clay, glues such as talcum powder and waxite powder, and silica powders such as aquatic earth and mica powder) Furthermore, alumina, sulfur powder, calcium phosphate, activated carbon, etc. are also used, and one or a mixture of two or more of these may be used.

Examples of ointment bases include polyethylene glycol (Fl(OCH2C)(2)nOH; n is 4 to 12.5), pectin, and higher fatty acids (carbon numbers 10 to 20) such as glycerol monostearate.
polyhydric alcohol esters, such as 7μrose derivatives such as methyμseμrose, a! One or two of sodium ginate, bentonite, higher alcohols, polyhydric alcohols such as glycerin, petrolatum, white petrolatum, liquid paraffin, liver fat, various vegetable oils, lanolin, dehydrated fluorine, hydrogenated oils, waxes, resins, etc. It is possible to select, as appropriate, one or more of these, or those in which various surfactants and the like are added.

In addition, surfactants used as emulsifiers, spreading agents, penetrating agents, and dispersants may be used in soaps, polyoxyamyl aryl ente/l/types (e.g., Nonar/I/■, Toho (manufactured by Kagaku), alkyl sulfates (e.g., Emer/L'lO■, Ema-/L'40■, manufactured by Kao Atlas), alkyl sulfonates (e.g., Neogen■, Neogun T■, Dai-Kogyo) fli!! 5>3 made by: Neoberetsukunu [F], Kao Atlas (L shelf), polyethylene glycol ether yv frequency (e.g., Noniho/L/85■, Nonibo/L'100■, Nonipole 160 [F], Polyhydric alcohol esters (eg, Tween 20[F], Tween 80■, manufactured by Kao Atlas Corporation) are used.

The plant disease control agent of the present invention can be used not only on plant seeds but also at any time from plant seedling to harvest. Not only can the onset of the disease be prevented by treating the plant with the Cnificide composition of the present invention before the onset of the 4i disease, but it may also be treated on the plant immediately after the onset of the disease according to a conventional method.

The amount of the plant disease control agent of the present invention to be used depends on the growth stage, growth condition, type of disease, and disease state of the target plant.

Although it varies depending on the tR'i conditions such as the time of application or application method of the drug, the sum of compound CI) and compound [l) is 1.
Approximately 3 to 300 g per 0 are, preferably 10
It may be adjusted so that the weight is about 100g. Also,
The concentration used is such that the sum of the above active ingredients is approximately 10 to 11
000pp range. In addition, the method of use may be direct spraying, direct dusting, irrigation, or seed coating on plants. Furthermore, the amount, concentration, or method of use may be changed as appropriate, as long as it is used safely and effectively for plants. In addition, other types of fungicides (e.g., organochlorine fungicides, organophosphorus fungicides, benzimidazo-μ fungicides, copper fungicides, organic sulfur fungicides, pheno-μ fungicides, etc.) may be used as necessary. agent.

Amino acid-based stimulants, antibiotics, etc.), insecticides (natural insecticides, carbamate-based insecticides, organic phosphorus-based insecticides such as Bilemeroid, etc.), acaricides, nematicides, herbicides, plant growth Regulators, stabilizers, synergists, attractants, repellents,
Flavors, plant nutrients, fertilizers, various amino acids, low-molecular or high-molecular phosphates, etc. may be mixed as appropriate.
Additions to metals (e.g. copper chloride,
Copper sulfate, etc.) may be added.

Compound CI) used in the plant disease control agent of the present invention is
17 Produced by reacting a compound represented by the general formula xl (the symbols in the formula have the same meanings as above) and a compound represented by the general formula (%) In this reaction,
Compound (V) is usually used in an amount of 3 to 3 molar equivalent to compound [■].
Although about twice the molar amount may be used, preferably 1 to 1.
Use about twice as much. This reaction is usually carried out in a solvent in the presence of water. Preferably, it is carried out in a solvent that forms two layers: water and a water-immiscible solvent. Examples of solvents used in the reaction include aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as hexane and heptane, halogenated hydrocarbons such as dichloromethane and chloroform, diethyl ether, tetrahydrofuran, Examples include ethers such as dioxane, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile, and ketones such as nitrobenzene, nitromethane, acetone, and methyμethyμketone. The amount of water coexisting in the reaction is usually about 5 to 200% of the amount of solvent.
Weight percentages are used, preferably from about 30 to 100 weight percent. Further, the amount of water to be allowed to coexist is sufficient if it is used to the extent of 1 to 100 times the weight of the compound [■].

The reaction temperature is about 0 to 80°C, preferably about 0 to 50°C.
It is.

The reaction time varies depending on the raw materials, type of solvent, reaction temperature, etc., but is usually from several minutes to several hours.

Completion of the reaction can be easily determined by thin layer chromatography or the like.

Furthermore, compound CI) can be produced by reacting a compound represented by the general formula [the symbols in the formula have the same meanings as above] and compound (V).

In this reaction, Compound (V) may be used at a current μ to 3 times the current μ to Compound (TV), but from 1 to 1.
It is best to use about 2 times 7μ.

The reaction is usually carried out in the presence of a solvent. Examples of solvents used in the reaction include aromatic hydrocarbons such as benzene and toluene, fatty hydrogens such as hexane and heptane, halogenated hydrocarbons such as dichloromethane and chloroform, diethyl ether μ, tetrahydrofufun,
Ethers such as dioxane, esters such as ethyl acetate.

Examples include nitrites/I/s such as acetonitrile, ketones such as nitrobenzene, nitromethane, acetone, and methyl ethyl ketone, alcohols such as methanol, ethanol, propano-μ, isoglopano-μ, and the like. The reaction temperature is about 0 to 80°C, preferably about 0 to 50°C.
It is ℃. The reaction time varies depending on the raw materials used, the type of solvent, the reaction temperature, etc., but is usually about several minutes to several hours.

Compound CI) produced in this way can be prepared by means known per se, such as filtration, concentration, vacuum concentration, solvent extraction, dissolution,
It can be isolated and purified by crystallization, recrystallization, chromatography, etc.

The raw material compound (]I[) for the production of compound CI) can be obtained by a method known per se (for example, U, 8.P, 3,129=225 ; method described in JP-A-57-81461 etc.) K is produced accordingly. Specifically, compound commercials
``J is obtained by the method shown by the following formula (III) First, dichloromaleic anhydride (vi) and compound [■] are reacted to form a dichloromaleamino acid derivative [■].
] Manufacture.

In this reaction, compound (VI) is used in an amount of about 7 to 3 times the amount of compound [■].

This reaction is usually carried out in a solvent. Suitable solvents include hydrocarbons such as benzene, toluene, xylene, hexane and cyclohexane, hydrogen halides such as dichloromethane and chloroform, diethyl ether μ, and tetrahydropran.

Ethe-Ns such as dioxane, N-groups such as ethyl acetate, nitric/I/alcohols such as acetonitrile, ketones such as methethylketone and acetone, aliphatic (carbon numbers 2 to 20) such as acetic acid and propionic acid. An inert solvent such as μponic acid is used.

The reaction temperature is about 30 to 150 tC, preferably about 40 to 100C. The reaction is completed in about 30 minutes to 5 hours. The resulting compound [■] may be isolated or may be directly subjected to the next reaction without being isolated.

Compound (IN) is a compound obtained in this way [■
] is produced by subjecting it to a dehydration ring-closure reaction. This dehydration ring closure reaction is usually carried out in a solvent. As a suitable solvent, there may be used an inert solvent which is used when producing the compound [■] by the reaction between the above-mentioned compound (VI) and the compound [■]. The reaction temperature is about 40 to 150°C, preferably about 80 to 120°C.

This dehydration ring closure reaction may be carried out in the presence of a dehydrating agent.

Suitable dehydrating agents include acid anhydrides such as acetic anhydride, phosphorus pentoxide, and polyphosphoric acid, and thionichloride/+7. Acid chlorophytes such as phosphorus oxychloride, or combinations thereof with organic bases such as pyridine, etc., are used. When a dehydrating agent is used, the reaction temperature is about 20 to 100°C, preferably about 30 to 80°C.

The reaction time varies depending on the type of solvent, dehydrating agent, etc., but is usually about 1 to 5 hours.

Further, the starting compound (IV) can be produced according to a method known per se (for example, the method described in JP-A-53-23962).

Further, the raw material compound (IV) can be produced by fs production by reacting the intermediate raw material compound [■] for producing the raw material compound (ur) with a dehydrating agent under mild conditions.

Examples of dehydrating agents in this reaction include dicyclohexylcarbodiimide, diethylcarbodiimide, and the like.
Positive imides, organic bases such as pyridine, quinoline, and F-ethylamine, and chlorocarbonate/L/, and penceyl ρ.
Combinations of acid halides such as clophyte and pency μ bromide, or combinations of the above bases with acid halides such as phosgene, thionyl clophyte, thionyl bromide, and phosphorus oxychloride are used.

This reaction is usually carried out in a solvent. As a suitable solvent, the inert solvent used in the production of the above-mentioned compound CI[) is used. Reaction temperature 1 is carried out at about -50 to 30°C, preferably about -5 to 20°C.

The reaction time is usually about 30 minutes to 3 hours.

Compounds (, I[), (IV) and their intermediates obtained as in
It can be isolated and purified by concentration, vacuum concentration, solvent extraction, dissolution, crystallization, recrystallization, chromatography, etc.

The compound [and] company itself is publicly known, for example, JP-A-50-1
40635. JP-A-55-7299, JP-A-50-1
35225. JP-A-50-135226, U, 8.
P, 3933860, JP-A-53-147061, JP-A-58-62144. G, B, P, 2070584,
LLaR4310463, U, aP, 4224453,
G, B, P, 2006783. Japanese Patent Publication No. 55-14727
It can be easily produced by the method described in 0 or a method similar thereto.

REFERENCE EXAMPLES AND EXAMPLES Next, the present invention will be explained in more detail with reference examples and examples, but the compounds, additives, and their blending ratios in the examples are not limited to these. Note that the percentages used in Examples and Test Examples are all percentages of M amount.

(Production of compound (N)) Reference example I N-(3,5-dichloro-4-methoxyphenylene/l/)
-Preparation of dichloromaleimide 3,5-dichloro-4-methoxyaniline (11.5 g) is added to a solution of dichloromaleic anhydride (10 g) dissolved in glacial acetic acid (100 g) at room temperature. After heating under reflux for 2 hours, the mixture is concentrated, and the precipitated crystals are collected in a furnace. After washing with n-hexane, recrystallization from toluene-n-hexane yields Compound 13.5. Melting point 153-154°C Reference example 2 N-(3-chloro-4-difluoromethoxyphenyl 1v
) Production of dichloromaleimide 1'! 1 Dissolve diku p/I/maleic anhydride (11,79) in dichloromethane (100rt) and cool to below 10°C.
While stirring, 3-chloro-4-Schiffuolomethoxyaniline (13.6 g) is added dropwise. When the precipitated crystals were collected, M-<3-chloro-4-Schiff ρ olomethoxypheni ρ)-dichloromaleamic acid 19.49. Melting point 13
A temperature of 2.5-134°C is obtained.

The above dichloromaleamic acid (129) was mixed with acetic acid (100g
+/) K was added, heated and stirred at 80°C for 2 hours, and then allowed to cool. After adding water to this, the precipitated crystals are collected in a furnace and purified by silica gel column chromatography (developing solvent: chloroform) to obtain 4.8 g of the title compound.

Temperature: 147-148°C (Production of Compound CIV) Reference Example 3 Production of N-(2,6-dimethyphene A/)-cycloleutumaleimide N-(2,6-dimethyphenylene/L/)- Dichloromaleamic acid amide (23, (1), !'dichloroxylcarbodiimide (1aSg) carbon tetrachloride (300y/
) Add to the solution little by little. After stirring at room temperature for 3 hours, insoluble matter is removed in an oven, and the fl liquid is concentrated to dryness under reduced pressure at a low temperature (approximately 5 to 10°C). After loosening with n-hexane, the resulting crystals are collected in a furnace and washed with n-hexane to yield 200 g of the title compound (t).

Melting point: 83-85°C.
820(''-1 shows the absorption of the carbonyl group specific to isoimide rlffa.

(Production of compound CI)) Reference example 4 Production of N-ethyl-N-(4-methoxyphenylene/l/)-dichloromaleic acid diamide (compound 1fx12) N-(4-methoxyphenylated/I/)-dichloro Maleimide (81.6g) was dissolved in dichloromethane (21)K,
After adding water (100 g/) to this, a 70% aqueous ethylamine solution (19,39) is added. After stirring at room temperature for 2 hours, the mixture was separated, the methane layer was dried over anhydrous sodium sulfate, and the mixture was concentrated to dryness at a low temperature (about 5 to 10°C) under reduced pressure. Add ether/L/(500Illt) to the residue and collect the precipitated crystals. Recrystallization from ethyl acetate yielded the title compound 47.
6 g is obtained.

One point 160-161℃ (dec, ) IR (Nugeot IV') 3270, 1655σ-1
Elemental analysis value CHM as C engineering, H engineering 4N203C12 Calculated value e/J: 49.23 4.45 8.83 Actual value N: 49.50 4.42 9.02 Example 2 N-ethyl μmN-(3, Preparation of 5-diylolophenymu)-dichloromaleic acid diamide (compound &44)U-(3,S-dichloromethane/L/)-dichloroX7maleimide (108,89)'e dichloromethane
s/) and add water (200v/) to it. 1
A mixture of a 70% aqueous solution of ethylamine (22 g) and water (30*t) is added to this mixture while stirring and cooling at 5 to 20°C. After stirring at room temperature for 1 hour, the mixture was concentrated under reduced pressure at low temperature (approximately 5 to 10 tl) to distill off dichloromethane. Water is added to the residue, and the precipitated crystals are collected in a furnace. After washing with water, recrystallization from ethyl acetate/1/(400 s/) yields 8.7 g of the title compound. Melting point 194-19
5℃ (dec, ) Engineering R (nujo-/l/) 3350.3290,32
70°1682.16591? Kasumi-1 Elemental analysis value HN as Cl2H1ON202''14 Calculated value (c) 40.48 2.83 7. R7 actual measurement -40,732,73R,]O Reference example 5 N-ethyl71/-m?-(2 , 6-dimethymuphenymu)
-Preparation of dichloromaleic acid diamide (compound A34)
) and add water (Low/) to it. A 70% aqueous ethylamine solution (
Add a mixture of water (51d) and water (51d). After stirring for 30 minutes at room temperature, dichloromethane is distilled off under reduced pressure at a low temperature (approximately 5 to 10"C). The precipitated crystals are separated and mixed with water,
Wash with n-hexane. After drying, recrystallization from acetonitrile yields 2.7 g of the title compound.

Melting point 191-192t' C) IN Calculated value Vj: 53.35 5.12 8.89 Actual value FA: 53.47 485 8.90 Reference example 6 N-ethyl-N'-(3,5-dimethylphenylene) -Preparation of dichloromaleic acid diamide (compound 61) N-(3,5-dimethyphenyl)-dichlorocimaleimide (5011) was dissolved in dichloromethane (200%), and then cooled with water and 70% aqueous ethylamine solution. (129
) and water (89) is added. After stirring at room temperature for 3 hours, the precipitate was collected in a furnace and recrystallized from cyclohexane to obtain the title compound 33.29.

Melting point 193-194℃ (dec, ) IR (Nugeot A/) 3250.1655.164
5-1 Elemental analysis value C14H16N202 C'HN as C12 Calculated value ■ 53.35 5-12 8-89 Actual value (c) 53.49 5-19 9.14 Reference examples 3 to 6 above
Compounds produced in the same manner as above are shown in Table 1, including the above compounds.

Table 1 Example 1 Wettable powder compound dynamic magnetism 16 2596. N-(2,6-dimethylphenylene/I/) -N-(2-fury/L/)anninemethyester A/2511N, sodium chloride naphthalene phosphate 396. Polyoxyethylene nonylphenythene/I/ak, white carbon 10% and calcium suboxide 29*t - homogeneously mixed and ground to make an irrigation agent. When using, dilute with water to the specified concentration and spray.

Example 2 Hydrating agent Combined magnetism 6825%, 2-chrome μmN-(2.

6-dimethy~pheny~> -X-(:tetrahydro-2
-oxo-3-fufni/l/) acetamide 25%.

Aμkiμnaphthalene〃sodium phonate 4 g 6゜Polyoxy V ethylene nonylphenylphenyl ether, /l/7*.

White carbon 10g6 and return acid power lvv 29%
It is mixed and pulverized uniformly to make an irrigation agent. When using, dilute with water to the specified concentration and spray.

Example 3 Emulsion compound Nagi 68 2551F, 3-chloro μ-N-(tetrahydro-2-oxo-3-phenolv) cycloprobanca μ boxyanilide 15%, xylene 55%, yN lyoxyethylene alkyμ aryl ade, /L15 An emulsion made by uniformly mixing %. Dilute appropriately with water before use.

Example 4 Powder compound Na55 1.5%, N-(2,6-dimethyμpheny/L/)-N-(methoxyacetyl/%/)afunin methyμ ester 1.0%, clay 40%.

Powder obtained by uniformly mixing and pulverizing 57.5% of Ruri.

Effect of bacterial load Test examples will be shown below to explain the effects of the present invention in detail.

Test Example 1 Residual efficacy test for controlling late blight on tomato (a) Test compound Compound [technique]: Compound tip 16, 19, 20° 40.44
．． 51.55.62゜68 and 69 Compound [■]: N-(2,6-dimethylphenyl/L')-N-(methoxyacetylenafnin methylesterμ (hereinafter referred to as compound A)
); N-(2,6-dimethy~pheny/I/) -N-(2-
Floy/L/) afnin methylesterμ (hereinafter abbreviated as compound B); 2-chloroμ-N-(2,6-dimethyμpheny/I/)-
N-(tetrahydro-2-oxo-3-furani/L/)
Acetamide (hereinafter abbreviated as Compound C); and 3-chloro-N-(tetrahydro-2-oxo-3-fufuni/I/)cycloprobanka μboquinanilide (hereinafter abbreviated as Compound Ri) (b) Test method sample Compound CI) was used as a test compound in the same manner as in Example 1.
and Compound (I[,)] is prepared, this water use agent is diluted with water to a predetermined concentration, and further KO
, Q3v/v% of the spreading agent Dyne [Takeda Pharmaceutical Co., Ltd.
Co., Ltd.] and placed this 50di in a greenhouse (20 to 30°
In C), the mixture was sprayed using a spray gun for 6 weeks on IIf diameter 15 alt pot-grown tomatoes (variety "Oinashi Fukuyo' 4-5 leaf seedlings)".

After spraying the chemical and keeping it in a greenhouse (20-30"C) for 7 days, the tomato late blight bacterium [P.
hytophthora 1nfestans),
Spray inoculation with 1 spore suspension (10 spores/dew liter), further kept at 17°C, 9 relative humidity & 100*Oi room, fli46
After several days, the lesion area rate (%) was determined according to the Japan Plant Protection Association survey standards.
)′f: Investigate and determine the control value.

The control value can be calculated from the formula below.

As a comparison, 25% of any one of the above test compounds
, polyoxyethylene alkyl aryte/L1
596, clay 70*t-A test is carried out in the same manner as above for the irrigation agent obtained by mixing.

The results (control value) are shown in Table 2.

How to read the above table: A compound ratio of 16 means a spray concentration of 125 when used as a single agent.
The control value is 9951 ppm, but the spray concentration is 62.5.
In ppm, the control value is 1.5g6. On the other hand, when the compound ratio of 16 is made into a mixture with compound A and the spraying concentration of each compound is 62 and 5 ppm, the control value is 100%. Furthermore, when Compound 416 is used as a mixture with Compound B, with Compound C, or with Compound Ri, and the spray concentration of each compound in the mixture is 62.5 ppm, the control value is 100*. show.

When compound A is used as a single agent, the spray concentration is 125 pp.
Control value: 43.0 m, spray concentration: 62.5 ppm
The control value is 096, and when compound B is used as a single agent, the spray concentration is 125 pp.
Control value: 29.1 m, spray concentration: 62.5 ppm
The control value is 0, and when compound C is used as a single agent, the spray concentration is 125 pp.
X11 Te control value aO, a Qin, spraying concentration 62.5 ppm
The control value is 0 or better, and when the compound is used as a single agent, the spray concentration is 125 pp.
Control value: 32.55M, spray concentration: 62.5ppm
indicates a control value of 0%.

The same applies to compounds other than Compound Style 16, and Tables 3 to 7 of Test Examples 2 to 6 have the same meanings as above.

Test Example 2 Cucumber and disease control test (test) Test compound Compound [technique]: Compound magnetic flux 16, 19.20° 40.44
, 55.68 and compound [■]: Compound A * B , C and D ('b)
Test method As a test compound, a compound [technique] was prepared in the same manner as in Example 1.
and Compound (II), diluted with water to a predetermined concentration, and further diluted with water to a predetermined concentration.
Spreading agent Dyne [Shikiyakuhin Kogyo Co., Ltd.] was added at a ratio of 3V/V%t to 10m/volume of the chemical solution for two weeks in a greenhouse (20 to 30°C).

Spray with a spray gun on a single cucumber (variety, four-leaf) grown in a pot with a diameter of 6 aa.

Cucumbers and diseased bacteria [Pseudoperonosporacube
Spray inoculation with a spore suspension (10 spores/st'') of S. nsis ) and keep in a greenhouse at 17°C and 100% relative humidity for 24 hours. After that, keep in a greenhouse (20 to 30°C) for 6 days. Based on the Plant Protection Association survey standards, the lesion area rate (9
6) Conduct a t-investigation and determine the KX control value using the calculation formula shown in Test Example 1.

As a comparison, 25g6 of any one of the above test compounds
, Polyoxyethylene μAryμEte/L'5
*A test is conducted in the same manner as above using a wettable powder obtained by mixing 70% clay.

Results (control value) t-shown in Table 3.

Test Example 3 Cucumber scab control test 5) Test compound Compound [I]: Compound Wind 16, 19, 40゜55 and 6
8 Compound [■]: Compounds A, B, C, and D test compounds ° were mixed with compound CI) and compound (It) in the same manner as in Example 1.
A hydrating agent containing the above is prepared, this hydrating agent is diluted with water to a predetermined concentration, and the spreading agent Dyne (manufactured by Shikinichi Yakuhin Kogyo Co., Ltd.) is further added at a ratio of 0.03 V/V%. Using a spray gun, spray 10 d of the chemical solution to which cucumber (cultivar, Yotsuba) was grown in a 6c11 diameter pot for 2 weeks in a greenhouse (2G to 30°C).

24 hours after spraying the chemical solution, the cucumber scab fungus (Cladosporium cucumerinum) was detected.
umerj, num) ) spore suspension (105/5
Spray inoculation of
% in a greenhouse, and then kept in a greenhouse (2G to 30℃) for 3 days to investigate the lesion area ratio (gM) on the leaves of the leaves according to the Japanese Plant Protection Association survey standards, and the results are shown in Test Example 1. Calculate the control value using the formula.

As a comparison, 25% of any one of the above test compounds;
Polyoxygen V Ethylene μ Ary μ Ete Iv5*,
An irrigation agent obtained by mixing clay TO% is tested in the same manner as above.

Results (control value) t-shown in Table 4.

(Leaving space below) Test Example 4 Cucumber seedling damping-off control effect test 5) Test compound Compound [Technical]: Compound Na16, 19.40°55 and 68 Compound [■]: Compound A and D 6) Test method Test sample An emulsion containing compound CI) and compound (It) is prepared in the same manner as in Example 3, and diluted with water to a predetermined concentration. Separately, 91 pots in which the crab spore suspension was poured and incubated were poured over the pots and 10 ml of the semi-potted Nao chemical solution was applied to each pot. Processing 4-
After 5 hours, 910 seeds of four-leaf cucumber were sown per pot, kept in a greenhouse (20-30°C) for 7 days after sowing, and then the rate of diseased seedlings (96) was investigated and calculated using the formula shown in the bottom fertilizer. Calculate the control value from

As a comparison, 25% of any one of the above test compounds;
Polyoxyethylene alkyl μary μate/L'5%
The same test as for the upper rudder was conducted on an irrigation agent obtained by mixing 70% clay.

Results (control value) t-shown in Table 5.

Table 5 Cucumber damping-off control effect test example 5 Cucumber secondary pox control test Test compound Compound [Work]: Compound Nagi 16.40 and 44 compound [■
]: Compounds A and D (b) Test method Prepare an irrigation agent containing compound CI) and compound [In using the test compound in the same manner as in Example 1, and add this irrigation agent to a predetermined concentration with water. Dilute to 0.03v/
A cucumber (1 plant) was grown in a pot with a diameter of 5 cm in an amount of 10 d of a chemical solution containing the spreading agent Dyne (manufactured by Ota Pharmaceutical Co., Ltd.) at a ratio of v* for 2 weeks in a greenhouse (20 to 30"C).
Spray on varieties, art collections) with a spray gun.

24 hours after spraying the chemical solution, the cucumber gray pox pathogen (Colletotric Colle A-lagnarium) was detected.
totrichu )) spore suspension (5XTO/
ml) was spray inoculated and kept at 17°C and relative humidity 10 for 24 hours.
0% greenhouse, then further greenhouse (20 to 30℃)
25% of one of the above test compounds, 25% of the above test compound, A test was conducted in the same manner as above for an irrigation agent obtained by mixing polyoxyethylene ethylene acyl aryl ether/l 1596 and 70% clay.

The results (control value) are shown in Table 6.

Test Example 6 Rice Blast Control Test ω Test Compound Compound [Technical]: Compound Magnetic Motion 40 and 50 Compound [■]: Compounds A and D Cb) Test Method The test compound was treated with Compound CI in the same manner as in Example 1. ) and compound (IF), diluted with water to a predetermined concentration, and further diluted with 0.03V/V.
Add the spreading agent Dyne (manufactured by Ota Pharmaceutical Co., Ltd.) at a ratio of 96% and 10d amount of the 96% solution to 4% in a greenhouse (20 to 30°C).
Spray it with a spray gun to 93 rice seedlings planted in bottlings that have been cultivated for a week. After the chemical solution dries, the rice blast fungus Pyricularia oryzae
ae) spore suspension (105/111) was inoculated by spraying. 2 days 25 to 30℃, relative humidity TO~+005
! ! f inoculation box and then placed in a greenhouse (20 to 30°
C) move inside. Seven days after inoculation, the lesion area ratio of the entire rice seedlings planted in pots is investigated according to the Japanese Plant Protection Association survey standards, and the control value is determined from the formula shown in Test Example 1.

As a comparison, 25g6 of any one of the above test compounds
, polyoxyethylene alkyl/l/ari-! Ete/L
15*, and an irrigation agent obtained by mixing Clay 7096 was tested in the same manner as above.

The results (control value) are shown in Table 7.

Table T Rice blast control effect test example 7 Tomato late blight control test The test chemicals shown in Table 8 were diluted with water to a specified concentration, and the spreading agent Dyne was added at a ratio of 0.03 V/V*. A chemical solution containing Illi from Yakuhin Kogyo Co., Ltd. was sprayed on tomatoes (6-week seedlings) planted in 80+/l-diameter 12α pots.

Twice a day from 2 days to 7 days after chemical spraying, 1 dose per time.
．． Perform artificial rain treatment at 5u/1 minute. Seven days after spraying, the leaves are cut and inoculated with a spore suspension of Phytophthora blight (10 spores/gl). At the same time, a no-rainfall area is established and treated in the same manner as above.

Five days after inoculation, the lesion area ratio (96) is investigated according to the Japanese Plant Protection Association investigation standards.

Results (lesion area ratio) 1-shown in Table 8.

(Margin below) Table 8 Tomato late blight control effect

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R is a hydrogen atom, a lower alkyl group, a lower halogenoalkyl group, or a lower alkenyl group,
, X_3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower halogenoalkoxy group, or a halogen atom, respectively] and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Ar is a halogen atom R_1 is a phenyl group substituted with , R_2 and R_3 each represent a lower alkyl group, or R_2 and R_3 taken together represent a group represented by the formula -(CH_2)_n- (wherein n represents 2 or 3). A plant disease control agent characterized by containing the following.